Drastic oxidation products of unsaturated fatty acid esters of oxyalkylated phenol-aldehyde resins



Patented Jan. 8, 1952 DRASTIC OXIDATION PRODUCTS OF UN- SATURATED FATTYACID ESTERS OF OXY- ALKYLATED PHENOL-ALDEHYDE RESIN S Melvin De Groote,University City, and Bernhard Keiser, Webster Groves, Mo., assignors toPetrolite Corporation, Ltd., Wilmington, Del., a corporation of DelawareNo Drawing. Application April 22, 1949, Serial No. 89,141

8 Claims. (01. 260-19) The present invention is concerned with certainnew chemical products, compounds or compositions which have usefulapplication in various arts. This application is a continuation-in-partof our co-pending application Serial No. 751,614, filed May 31, 1947,and now abandoned. Atten tion is also directed to our co-pendingapplication Serial No. 64,469, filed December 8, 1948, and also ourapplication Serial No. 30,184, filed May 29, 1948.

This invention includes methods or procedures for manufacturing said newchemical products, compounds, or compositions, as well as the products,compounds, or compositions themselves. Said new compositions aredrastically-oxidized esters in which the acyl radical is that of anunsaturated monocarboxy acid having at least 8 and not more than 22carbon atoms, and the alcoholic radical is that of certain hydrophilepolyhydric synthetic products; said hydrophile synthetic products beingoxyalkylation products of (A) An alpha-beta alkylene oxide having notmore than four carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide, andmethylglycide; and (B) an oxyalkylation-susceptible, fusible, organicsolvent-soluble, water-insoluble, phenolaldehyde resin; said resin beingderived by reaction be tween a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and reactive toward said phenol;said resin being formed in the substantial absence of trifunctionalphenols; said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in the 2,4,6 position; said oxyalkylatedresin being characterized by the introduction into the resin molecule ofa plurality of divalent radicals having the formula (R1O)n, in which R1is a member selected from the class consisting of ethylene radicals,propylene radicals, butylene radicals, hydroxypropylene radicals, andhydroxybutylene radicals, and n is a numeral varying from 1 to 20; withthe proviso that at least 2 moles of alkylene oxide be introduced foreach phenolic nucleus; and with the final proviso that said dras ticoxidation of the ester be by means of a gaseous oxygen-containingmedium.

1 Although the herein described products have a number of industrialapplications, they are of particular value for resolving petroleumemulsions of the water-in-oil type that are commonly referred to as cutoil, roily oil, emulsified oil, etc., and which comprise fine dropletsof naturally-occurring waters or brines dispersed in a more or lesspermanent state throughout the oil which constitutes the continuousphase of the emulsion. This specific application is described andclaimed in our co-pending application Serial No. 89,140, filed April 22,1949, now Patent 2,542,008, granted Feb. 20, 1951. See also ourco-pending application Serial No. 64,468, filed December 8, 1948, andnow abandoned.

The new products are useful as wetting, detergent and leveling agents inthe laundry, textile and dyeing industries; as wetting agents anddetergents in the acid washing of building stone and brick; as wettingagents and spreaders in the application of asphalt in road building andthe like; as a flotation reagent in the flotation separation of variousaqueous suspensions containing negatively charged particles, such assewage, coal washing waste water, and various trade Wastes and the like;as germicides, insecticides, emulsifying agents, as, for example, forcosmetics, spray oils, water-repellent textile finishes; as lubricants,etc.

The oxyalkylated resins, used to provide the alcoholic radical of thenew esters, are described in our Patents 2,499,370, granted March 7,1950, and 2,542,008, granted February 20, 1951, and reference is made tothese patents for a description of phenol-aldehyde resins to produce thealcoholic products. For specific examples of the resins, reference ismade to Examples 1a through 103a of Patent 2,499,370. For examples ofoxyalkylatedproducts derived from these resins, reference is made to thetables at columns 31 through 46 of Patent 2,542,008.

Having prepared or purchased suitable oxyalkylated derivatives to beused as alcoholic re actants, one can purchase or prepare variousmonocarboxy detergentforming acids characterized by the fact that theyhave at least 8 and not more than 22 carbon atoms. The next step is toprepare the esters of such monocarboxy detergent-zforming acids and thescribed oxyalkylated derivatives. The final step, after the preparationof the esters of the kind Just described, is to subject them to drasticoxidation by means of a gaseous oxygen-containing medium, such as air,ozone, etc.

Reference is made to our co-pending application, Serial No. 64,454,filed December 8, 1948,

previously denow patent No. 2,541,9s5 issued February 2D. 1951. Saidco-pending application describes esters of the kind herein employed asintermediates, i. e., subjected to drastic oxidation. Saidaforementioned application contemplates not only esters of unsaturatedfatty acids, but also other esters, including saturated fatty acids. Aspreviously stated, the monocarboxy detergent-forming acid esters hereinconteni plated are limited to those derived from unsaturated fatty acidshaving 8 to 18' carbon atoms, and particularly those which have 18carbon atoms. Such unsaturated fatty acids include oleic acid,ricinoleic acid, linoleic acid, linolenic acid, undecylenic acid, etc.One may employ mixed fatty acids, as, for example, the fattyacidsobtained from hydrolysis of cottonseed oil, soyabean oil, sunflowerseed oil, dehydrated castor oil, etc.

ester, one need not use the acid itself for the introduction of the acylor acyloxy group.

As it is well known, the production of an 1944, insofar that theydescribe the production of esters of certain unsaturated fatty acids,and more particularly, drying oils involving alcoholic bodies which areessentially the same hy-- droxylated reactants, as herein described.

It will be noted that having obtained a compound which is essentially apolyhydricalcohol, i. e., an oxyalkylated resin of the type herein con--templated, one can produce esters byany one of the various proceduresemployed for producing esters of detergent-forming acids and the morecommon polyh-ydric alcohols. As is well known, one may well employ notonly the fatty acid itself, but any suitable derivative, for instance,the acyl chloride, the anhydride, etc. In

some instances, trans-esterification or cross-ea terification can beemployed. For instance, the

oxyalkylated derivatives can be heated with the ethyl or methyl ester ofthe selected acid in presence of an alkaline catalyst so as to eliminatemethyl or ethyl alcohol, Such procedure is particularly desirable when ahydroxylated acid is used, such as ricinoleic acid, etc. Trans-ester?fication or cross-esterification can be employed in connection with aglyceride with the forma tion of glycerine, which, under conditions ofreaction, probably polymerize to give polyglycerols and thus gives asignificant and many times a major proportion of the desired ester. Itwill be noted that part of what is said herein in regard toesterification and particularly in regard to the earlier examples, iscomparable to What is said in our aforementioned co-pending applicationSerial No. 42,138, filed August 2, 1948, which, as previously stated, isa continua-' tion-in-part of our now abandoned applications Serial Nos.518,660 and 518,661, both filed January 17, 1944.

As a rather complete review of the preparation of polyhydric alcoholesters of fatty acids, see Chemical Review 33 257-349 (1943).

Example 10 An oxyalkylated derivative, such as Example 1211) of Patent2,542,0(38, is esterifled with soyabean oil fatty acids in an amountsufiicient to convert approximately one-fourth of the polyglycolradicals into the fatty acid ester. The hydroxyl value of theoxyalkylated derivative can be calculated without determination, basedon the hydroxyl value and weight of the phenolaldehyde resin originallyemployed, plus the increase in weight after oxyalkylation. If glycide ormethylglycide is employed, allowance must be made for the polyhydriccharacter of the oxyalkylating reactant. In any event, if desired, thehydroxyl value of the oxyalkylatcd product can be determined by theVerley-Bolsing method, or any other acceptable procedure. The esterification reaction is conducted in any conventional manner, such asthat employed for the preparation of the higher fatty acid esters ofphenoxyethanol.

Fatty acids, and particularly unsaturated fatty acids, show at leastsome solubility in the oxyalkylated derivatives of the kind shown in theprevious examples, even though this is not necessarily true of theglycerides of the fatty acids. In this instance, reference is inade tothe oxyalkylated derivatives in absence of a solvent. Sinceesterification is best conducted in a system, it is our preference toadd xylene or even a higher boiling solvent, such as mesitylene, cymene,tetralin or the like, and conduct esterification in such consolutemixture. It is not necessary to add all the fatty acid at one time. Onemay add a quarter or half the total amount to be esterified, and aftersuch portion of the reactant has combined, then add more of the fattyacid. The solubility of the fatty acid, of course, increases as thehydroxyl radical is replaced by an ester radical. This is also true ifone resorts to transesteriiication or cross-esterification with theglyceride or low molal alcohol ester.

Our preference is to have present a substantial amount of xylene orhigher boiling, waterinsoluble solvent, and to distill under refluxcondenser arrangement so that water resulting from esterificaticn isvolatilized and condensed along with the xylene vapor in a suitablyarranged trap. The amount of xylene employed is approximately equal toone-half the weight of the mixed reactants. The water should be removedfrom the trap, either manually or automatically, and the xylene returnedcontinuously for further distillation. Such reaction is hastened if asmall amount of dry hydrochloric acid gas is continuously injected intothe esterification mixture. When the reaction is completed, the xyleneis removed by distillation. Small amounts of unreacted fatty acid can beconverted into the methyl or ethyl ester and removed by vacuumdistillation, or permitted to remain. For example, an excess ofanhydrous ethyl alcohol can be added, and reacted so as to esterify anyresidual fatty acid, and then such excess of ethyl alcohol may bedistilled off as 95% of alcohol-5% of water mixture; and thus, the waterresulting from esterification with the alcohol can be removed. Althoughany residual fatty acid can be eliminated in the manner above described,this is of limited importance, except if one were preparing a drying oilfatty acid derivative which would ultimately find use in varnishproduction. In such instances elimination of all fatty acid is importantto give enhanced alkali resistance.

However, even where the amount of fatty acid employed isstoichiometrically equal to the hydroxyl radicals present, we have notfound it desirable to take any undue precaution to eliminate anyresidual fatty acid. As a matter of containing resin of Example 121!) ofPatent 2,542,008 were reacted with 71 .grams of soyabean fatty acid inthe presence of 300 grams-of additional xylene and grams of para-toluenesulfonic acid. Reflux was continued for 3 hours,

or until 4.5 grams of water had been evolved.

Example 20 The same procedure was followed as in Example lc, preceding,except that the amount of soyabean oil fatty acids employed wassufficient to convert one-half the polyglycol radicals into ester form.

As a specific example, 854 grams of the xylenecontaining resin 116b ofPatent 2,542,008 were reacted with 142.3 grams of soyabean fatty acidsin the presence of 200 grams of additional xylene and 15 grams ofpara-toluene sulfonic acid at" 140 C. until 9 grams of water had beenevolved. This took about 4 hours.

Example The same procedure was followed as in Example 1c, preceding,except that the amount of soyabean oil fatty acids employed weresufiicient to convert three-fourths of the polyglycol radicals intoester form.

As a specific example, 511 grams of the xylene Example 40 The sameprocedure was followed as in Example 1c, preceding, except that theamount of soyabean oil fatty acids employed was sufiicient to convertsubstantially all of the polyglycol radicals into ester form.

As a specific example, 900 grams of the xylenecontaining resin 1211) ofPatent 2,542,008 were reacted with 85.6 grams of methyl oleate in thepresence of 200 grams of additional xylene and 2 grams of sodiummethylate. After heating four hours at reflux (146 C.-148 C.) about 32grams of ethyl alcohol had been recovered by aqueous extraction from thexylene in the D-S tray. The xylene was returned to the reaction vessel.

Example 'The same procedure was followed as in Examples 10 to 40,preceding, except that the oxyalkated derivative, instead of being thekind exemplified under the heading of Example 12112 of Patent 2,542,008,was a resin exemplified by either Example 1061) or 1321) of Patent2,542,008.

Example The same procedure was followed as in Examples 1c to.4c,preceding, exceptthat the-oxyin the elimination amples 1c to 60,

flower seed oil, or the like.

amplesalkylated thermoplastic phenolaldehyde resin was one of the typeexemplified by Examples 10Gb to 120b, of Patent 2,542,008, instead ofone of the type exemplified by. Examples 12% to 14012 of Patent2,542,008, inclusive.

Example 7c The same procedure was followed as in Expreceding, exceptthat soyabean oil fatty acid was replaced by other unsaturated fattyacids, such as linoleic or linolenic or the mixed fatty acids obtainedfrom peanut oil, sun- The diene fatty acids obtained from dehydratedcastor oil may be employed.

Example 8c The 'same procedure was followed as in Ex- 10 to Sc,preceding, except that instead of employingsoyabean oil fatty acid, amarine oil fatty acid such as the fatty acids obtained from hydrolysisof menhaden oil, is employed.

Example The same procedure was followed as in Examples 10 to 60,preceding, except that instead of Example The same procedure wasfollowed as in the preceding examples, except that the reaction wasconducted by means of the ethyl or methyl ester instead of the fattyacid. The reaction was conducted preferably in the absence of anysolvent, or if a solvent is employed, it should be fairly high boiling,such as xylene. Instead of using an acid catalyst, an alkali such ascaustic soda or sodium methylate was employed. The amount used variesfrom one-tenth of 1% to 1%. An average value may be in the neighborhoodof one-half of 1%. The reaction was conducted preferably with the methylester, which results of methanol. In the presence of a solvent such asxylene, the methanol might distil over with the xylene, and if so, canbe removed by washing with water, followed by removal of any moisturefrom the xylene, with subsequent return of xylene to the reactionvessel. However, any suitable procedure and any suitable catalyst may beemployed so as to form the ester by elimination of a low molal alcohol,particularly methanol. The series of preceding examples, to wit,Examples 10 to 90, inclusive, usedvarious fatty acids. These should bereplaced with a molecular equivalent of methyl oleate, methylricinoleate, methyl linoleate, etc.

Example The same procedure was followed as in the preceding examples,except that the ester was produced by cross-esterification ortrans-esterification employing a glyceride so as to result in theformation of a non-volatile alcohol instead of a volatile alcohol as inExample 100, preceding. The catalyst used was an alkaline catalyst andthe temperature employed was approximately 200 to 225 C. The time ofreaction may vary somewhat, but generally requires 3 to 8 hours. Thetemperature should be high enough to assure trans-esterification inpresence of the alkaline catalyst; but in any event, should be below thepoint of pyrolysis, as far as the oxyalkylated derivative or fatty acidis concerned. As a rule, pyrolysis may take place at any temperatureabove 250 C. In the preceding Example 100, the fatty acid was replacedby an equivalent molar proportion of the methyl or ethyl ester. In thisinstance it was replaced by an equivalent molar proportion of glyceride,and particularly the glyceride in the form of a naturally-' occurringoil. Our preference is to use triolein, tristearine, triricinolein,linseed oil, castor oil,

- Resin Resin Ex. a Fatty RT.

Sol Water Ex. 0. of Xylene Acid, S. A., Temp, Time,

No. Patent fi in Add Used Wt., We, 0. g hrs.

A 2,542,008 Grams Grams Grams 11111 400 77.4 93. 4 '20 145 10. 7 6%1221) 300 71. 3 71. 5 20 145 6.1 254 133i: 300 44. 7 e2. 5 2o 142 2. e 5E36!) 300 50 103. 2 15 148 9. 2 5 1106b 300 61. ti 190. 2 20 151 ll.i231) 300 37. 8 70. 8 20 1-15 8. 3 6% 11711 300 54. 6 79. 0 20 152 9. 08% 11% 300 48. 2 63. 8 20 148 5. S 7% 113!) 300 -19. 0 63. 8 20 148 5. e7% 121!) v 300 71. 5 101. 9 20 149 3. l 5% I23?! 300 45. 1 65.1 20 1475. l 2% 1316 300 51. e 99. 0 20 147 6.0 3% 1371) 300 50. 0 0410--.. 68.8 146 5. 8 4% 117i) 300 54. 6 Ricinoleic. 83. 5 144 6. 6 6}; 112!) 30062. 5 79. l 20 147 8. 3 6% 132!) 300 53. 5 78. 2 10 148 2. 0 2%. 137b300 82. 8 15 148 3. 9 43 3 121!) 300 71. 5 100. 0 20 146 4. (i 5parative ease, whereas, the hydroxyl radicals of the oxyalkylatedderivatives may etherize to a lesser degree. There is also thepossibility that in partthe glycerol may etherize with the oxyalkylatedderivative. This brings about the same result as if the oxyalkylatedderivate had been treated with a mole of glycide as a terminal reactant.

We have prepared a large number of esters from a variety of unsaturatedfatty acids and. also from a variety of mixed fatty acids obtained bythe hydrolysis of various fats or oils Without an effort to separatesuch mixtures. We call particular attention to the fatty acids availablefrom various sources, such as those prepared by Armour & Company andsold under the trade name of Neo-fat fatty acids. These are describedcompletely in a booklet distributed by the Chemical Division of Armour82 Company, Chicago. Illinois. We make particular reference to Neofat 3,Neofat 3R, Neofat S142, Neofat D142, Neofat l9, Neofat 23, DD CottonseedFatty Acids, DD Corn Oil Fatty Acids, DD Soyabean Fatty Acids, and DDLinseed Fatty Acids.

Some of the fatty acids which give particularly valuable products areenumerated in the following table. The first column indicates theexample number; the second column indicates the specific oxyalkylatedresin employed and previously described; the third column indicates theamount of resin solution employed, including the xylene present as asolvent; the fourth column. indicates the amount of xylene present inthe correspondingdtem in the previous column;

One rather peculiar property is the fact that where some of theoxyalkylated resins show moderate or limited solubility in water priorto esterification, particularly in the manner last indicated, theysometimes seem to show even greater solubility in water after suchesterification process, notwithstanding the fact that apparently a largehydrophobe radical is introduced, and in essence, the repetitiousalkylene oxide linkage apparently must solubilize both hydrophoberadicals, i. e., the one derived from the resin and the one derived fromthe unsaturated higher fatty acid.

It has been pointed out previously that the oxyalkylated resins varyfrom semi-solids or solids, or sticky solids, to liquids, showing littleor no viscosity, or, in any event, viscosity no greater than that ofcastor oil. Needless to say, if a solvent such as xylene is present, theviscosity is reduced and the solution of a solid may become a liquid.The Water-soluble or dispersible characteristics of the oxyalkylatedresins have been described previously in detail; also theirsurface-activity or sub-suriace-activity. The color of theseoxyalkylated resins varies from almost colorless to deep amber, darkbrown, or black, or reddish-black. The esters produced show the samevariation, except, as a rule, the color becomes darker, partlcularlywhen para-toluene sulfonic acid is used as a catalyst, and particularlyif the air is not excluded during esterification. The solubility inwater, or dispersibility, is almost invariably reduced by theintroduction of a sizable hydrophobe group. In some instances, thisreduction in water solubilit or water dispersibility does not seem totake place. As the materials become esterified, there is a tendency toreduce the viscosity, as far as going from solids to semi-s0lids orliquids go, or as far as tackiness goes. In some instances where theoxyalkylated derivatives are liquids prior to esterification, thereseems to be no change in viscosity, or, at least, a modest increase.Experience has indicated that practieallyall. ormany, or these productscan be bleached with clays, charcoal or the like, to produce productswhich are much lighter in color, and, if desired, the solventpresent, 1. e., xylene, can be removed by distillation, and particularlyvacuum distillation. For purposes of preparing derivatives to be used indemulsification, these steps are unnecessary and the products preparedas described are very effective. This is also true of application inother arts.

Havin obtained unsaturated fatty acid esters of the kind described, theyare subjected to drastic oxidation in much the same way that is employedin producing blown castor oil, blown soyabean oil, blown neats-foot oil,etc. It is well known that oxidized oils can be obtained from castoroil, ricinoleic acid, and various derivatives of ricinoleic acid, suchas monoricinolein, diricinolein, and polyricinoleic acid. They areproduced by the common practice of.blowing or oxidizing castor oil andsimilar fatty oils or acids, particularly non-drying unsaturated fattyoils, by means of a gaseous medium, such as air, oxygen, ozone, orozonized air. The gaseous medium, such as air, may be moist or dry andthe oxidation may take place in the presence or absence of a catalyst.The catalyst may be of a metallic type, such as lead ricinoleate, cobaltricinoleate, manganese ricinoleate, etc., or it may be of the organictype which produces peroxide such as alpha-pinene, linseed oil, etc.Oxidation may take place at atmospheric pressure or superatmosphericpressure, i. e., pressures up to or including 200 pounds gauge pressure,and at any temperature slightly above the boiling point of water, forinstance, 120 0., up to any temperature which does not produce unduedecomposition by pyrolytic reaction.

The time of blowing may be fairly brief, for example, 8-10 hours; or itmay be quite extentive, for instance, as long as 10-1-2-14 days, thelonger time periods being employed generally when the temperature isjust slightly above the boiling point of water, and when oxidation iswith air at atmospheric pressure.

One method of preparing drastically-oxidized castor oil is described inU. S. Patent No. 2,023,- 979, dated December 10, 1935, to Stehr. Also,see U. S. Patent No. 2,183,487, dated December 12, 1949, to Colbeth.

In our previously mentioned co-pending application Serial No. 30,183,filed May 29, 1948 now Patent 2,498,656 issued February 28, 1950, wedescribed the oxidation of the hydrophile hydroxylated oxyalkylatedresins identified by numerals followed by the letter b, of whichtherehave been a large number of examples. In that particularapplication we were concerned with the same sort of drastic oxidationstep as herein employed, but with the oxidation of the polyhydricalcohol, as distinguished from the partial or complete ester. There isevery indication that, in addition to the oxidation of the fattymaterial which introduces complexities of the kind which are present inthe oxidation-of castor oil, there is also oxidation of the kinddescribed in our co-pending application Serial No. 30,183, filed May 29,1948. For this reason, and in order to shed greater light on this seriesof complicated changes which take place, the following is quotedverbatim:

This example (i. e., an oxidized unesterified oxyalkylated resin,particularly 1b) clearly illustrates the products obtained by drasticoxidation of the oxyalkylated thermoplastic phenol-aldehyde resinsemploying a gaseous oxygen-containing medium. The changes that takeplace are so marked that there is no question as to the nature of theproduct which has been subjected to oxidation. In the first place, thereis an enormous increase in viscosity; in fact, if drastic oxidaticn iscontinued, the entire mass becomes stringy, sub-rubbery, or rubbery, andinsoluble in any one of numerous solvents, such as xylene, diethyletherof ethylene glycol, or diethylether of diethylene glycol, or mixtures ofaromatic solvents and alcohols, such as butyl alcohol.

However, as soon as there is any marked change in viscosity there isalso a marked change in water-solubility, or in the hydrophile propertyof the compound. In other words, if one starts with an oxyalkylatedresin which shows selfemulsifiability prior to drastic oxidation, thisproperty will be reduced greatly or will almost disappear short of thesub-rubbery stage. If one employs an oxyalkylated resin which showscomplete water-solubility, then after drastic oxidation, this propertywill be largely lost or almost completely disappear. Suchdrastically-oxidized product still has some hydrophile characteristics,due to the obvious presence of oxygen atoms. Thus, the characteristic p1operties of the oxidized products are (1) reduced hydrophile property,(2) increased viscosity, and (3) indications that further oxidation mayreadily convert the product to a stringy or sub-rubbery stage. It mayseem that the properties previously noted could be related to esterformation. In other words, one could assume that oxidation converts someof the hydroxyl' radicals to carboxyl radicals, and these, in turn,esterify with some of the remaining hydroxyl radicals to produce esters.Such cross-linking would, of course, account for properties of the kindpreviously described, if such esterification did take place. However,chemical examination of the drasticallyoxidized product indicates littleor no increase in either the acid number, or in the saponificationnumber, at least insuincient to account for the change. Thus, as onewould expect, saponification does not regenerate the correspondingparent type of material. It is possible that the change which takesplace involves formation of ether linkages between alkylene radicals orresidues.

In light of what has been said previously, it hardly appears necessaryto include any examples of the final drastically-oxidized ester.However, as a matter of convenience, the invention may be illustrated bythe following examples:

Example 1d A thermoplastic resin is prepared from amyl or butyl phenoland formaldehyde in the manner previously described and illustrated bypreceding examples. Such resin is then divided into three parts and oneportion treated with ethylene oxide equal to 1 /2 times the Weight ofthe resin. The second portion is treated with ethylene oxide equal tothree times the weight of the resin. The third portion is treated withethylene oxide equal to 4 times the weight of the resin. Each of thesethree portions is reacted with the ethyl or methyl ester of ricinoleicacid in presence of an alkaline catalyst, so as to eliminate the lowmolal alcohol and form the ricinoleic acid ester. Our preference is touse the stoichiometric amount so as to convert all the hydroxyl radicalsinto ester radicals. Each of the three esters thus obtained is subjectedto low temperature oxidation by means of air until the drastically-oxiaExample 2d The same procedure is followed as in the preceding example,except that the methyl or ethyl esters of soyabean fatty acid areemployed so as to introduce fatty acids of the kind which occurnaturally in soyabean oil.

Example 301 The same procedure is followed as in Example 1d, preceding,except that the methyl or ethyl ester of undecylenic acid is employed.Our experience has been that generally the period of oxidation must beextended approximately 25%, for the reason that these esters do notoxidize quite as rapidly as a rule.

Example 4d The same procedure is followed as in Example 101, preceding,except that the methyl or ethyl esters of rapeseed oil fatty acids areemployed.

Example 5d The same procedure is followed as in Example 1d, preceding,except that the esters derived from menhaden oil after partialhydroxylation by means of hydrogen peroxide, are employed.

Emample 6d The same procedure is followed as in Example 1d, preceding,except that the methyl or ethyl esters derived from dehydrated castoroil, are employed.

Example 711 The same procedure is followed as in the six previousexamples, except that a stoichiometric equivalent of propylene oxide isemployed instead of ethylene oxide.

It may seem, at first casual examination, that the same products couldbe obtained by esterifying the fatty acids of properly selected :blownoils with the oxyalkylated resins. Such is not the case apparently fortwo reasons. In the first place, converting blown glycerides of anykind, for instance, blown castor oil or blown dehydrated castor oil,into the corresponding methyl or ethyl ester, produces certain changesin structure, for the reason that such drastically-oxidied productscontain hydroxy acid esters thereof, anhydrides, and other compoundswhich are susceptible to change during saponiication or esterification.In the second place, the mere oxidation of oxyalkylated thermoplasticphenol-aldehyde resins herein described, produces certain changes whichare not understood, but which clearly affect the properties of suchmaterial, all of which is described in our co-pending application SerialNo. 30,183, filed May 29, 1948.

Referring to the large series of examples which have been produced anddescribed, preceding, we have preferred to do as follows in theoxidation stage. In the first place, after esterification, we have madeit a point to remove all the Xylene either permitting the xylene to becaught in the trap and removed, or else making the usual connection withthe condenser so as to remov the xylene or use a vacuum pump and atemperature up to or C. If desired, of course, the xylene can be left inthe mass, for the reason that as gaseous oxidation starts, the xylene isgradually removed by mere passage of air or the like. This, however,means an unnecessary loss of xylene, particularly on a large scale.Secondly, we prefer to neutralize any sulfonic acid present as acatalyst, adding just the required amount of the concentrated 25%caustic solution. In the following experiments which are tabulatedbelow, the particular esters employed are those which have beendescribed previously. in each cas we employed approximately 1,000 grainsof the ester and a temperature approximately 110 to 115 C. A continuousstream of air was passed through the mixture and the material oxidizeduntil there was a drastic change, as previously noted, 1. e., adarkening of the product along with a marked change in viscosity. inmost cases attempt was made to blow the products until they were asthick as possible without being livery or suggestive that they wouldshortly enter the gelation or semi-rubbery stage. The oxidationinvariably darkened the materials, increased their viscosity,

and, in fact, made them much more viscous and invariably darkened theproducts, and frequently they had a tacky or almost incipient tackynature.

In such case, however, the state of oxidation was stopped at such apoint that the final product was still soluble in a solvent,particularly xylene or the like. Furthermore, in all these particularexperiments listed in the table, and for that matter, the othersdescribed previously, the final products met the same qualification testfor presence of hydrophile properties previously noted in connectionwith the cxyalkylated resins themselves, i. e., the xylene solution,when shaken with water, produced an emulsification as previouslydescribed.

In the following table the first column indicates the example number;the second column indicates the particular ester previously described;the third column the amount of ester oxidized, which was generally 1,000grams; the fourth column indicates the temperature or oxidation whichwas generally in the neighborhood of 110 0.; the fifth column indicatesoxidizing agent used, which was air, without any attempt to dry the air;the sixth column shows the air stream rate. In the oxidation of a 1,000gram sample we have used a flask of approximately 3 liter capacity so asto allow room for a foam build-up without a carry over where thisoccurred. Also, it is quite possible that as foam build-up starts,oxidation takes place in the foam to a, considerable degree, rather thanin the mere passage of the air bubble through the liquid phase. We haveconsidered a slow rate as being one where we attempted to permit abubble to reach the top of the fluid before the next bubble appeared. Wehave considered a fast rate as one in which a multiplicity of bubblesare passed through as rapidly as possible without forcing the foam outof the oxidation flask. We have considered a medium rate as onesomewhere in between, i. e., a multiplicity of bubbles passing throughthe liquid layer at all times, but not in a stream sufficient to forcefoam out of the flask. This particular value is not critical.

The seventh column indicates the time of oxidation and generally lastsfrom 100 hours to about hours, or approximately five, six, or sevendays. The time is indicated in days.

The eighth column indicates the final appear 13 ance of the productwhich was"generally dark and highly viscous.

The ninth column indicates whether-or not the product is soluble inxylene, or, in some 14 that'the blowing of the ester be by means of agaseous oxygen-containing medium.

2. A blown ricinoleate of certain hydrophile polyhydric syntheticproducts; said hydrophile instances, more soluble in the diethyles'terof synthetic products being oxyalkylation products ethylene glycol, orthe diethyleste'r of diethyle'ne of (A) an alpha-beta alkylene oxidehaving not glycol. The word yes simply means that the more than 4 carbonatoms and selected from the sample did meet the solubility requirements.class consisting of ethylene oxide, propylene ox- Temp. of Solubil- Ex.Ex. No. Ox. Agt. An Stream Time, N0. of Ester Grams 056i Used Rate daysAppear. Final Prod. 11331 15531121] 8d 120 1.000 6 Darkincrcasedviscosity.. Yes. 90.. 130 1,000 it .....do Do. 10d. 16c 1,000 Do. 11d-180 1,000 Do. 12d. 100 1, 000 Do. 13. 1, 000 Do. 14d 210 1,000 Do. 15d.220 1,000 Do. l6d 1,000 Do. 17d. 200 1.000 Do. 18d. 290 1,000 Do.

l. A blown ester in which the, acyl radical is that of an unsaturatedfatty acid having at least 8 and not more than 22 carbon atoms, and.

the alcoholic radical is that of certain hydrophile polyhydric syntheticproducts; said-hydrophile synthetic products being oxyalkylationproducts of (A) an alpha-beta alkylene oxide having not more than 4carbon atoms and selected from the class consisting of ethylene oxide,propylene oxide, butylene oxide, glycide, and

methylglycide; and (B) an oxyalkylation-sus-a ceptible, fusible, organicsolvent-soluble, waterinsoluble, phenol-aldehyde resin; said resin beingderived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and having one functional groupreactive toward said phenol; said resin being formed in the substantialabsence of phenols of functionality greater than 2; said phenol being ofthe formula in which R is a hydrocarbon radical having at least 4 andnot more than 12 carbon atoms and substituted in one of the positionsortho and para; said oxyalkylated resin being characterized by theintroduction into the resin molecule at the phenolic hydroxyls of aplurality of divalent radicals having the formula (R10) n, in which R1is a member selected from the class consisting of ethylene radicals,propylene radicals, butylene radicals, hydroxypropylene radicals, andhydroxybutylene radicals, and n is a numeral varying from 1 to 20; withthe proviso that at least 2 moles of alkylene oxide be introduced foreach phenolic nucleus, and with the final proviso ide, butylene oxide,,glycide and methylglycide; and (B) an oxyalkylation-susceptlble,fusible, organic solvent-soluble, water-insoluble phenolaldehyde resin;said resin being derived by reaction between a difunctional monohydricphenol and an aldehyde having not over 8 carbon atoms and having onefunctional group reactive toward said phenol; said resin being formed inthe substantial absence of phenols of functionality greater than 2; saidphenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in one of the positions ortho and para;said oxyalkylated resin being characterized by the introduction into theresin molecule at the phenolic hydroxyls of a, plurality of divalentradicals having the formula( R10) n, in which R1 is a member selectedfrom the class consisting of ethylene radicals, propylene radicals,butylene radicals, hydroxypropylene radicals, and hydroxybutyleneradicals, and n is a numeral varying from 1 to 20; with the proviso thatat least 2 moles of alkylene oxide be introduced for each phenolicnucleus; with the further proviso that the hydrophile properties of theester as well as the oxyalkylated resin in an equal weight of xylene aresufiicient to produce an emulsion when said xylene solution is shakenvigorously with one to three volumes of water; and with the finalproviso that said blowing of the ester be by means of a gaseousoxygen-containing medium.

3. A blown ricinoleate of certain hydrophile polyhydric syntheticproducts; said hydrophile synthetic products being oxyethylationproducts of (A) ethylene oxide; and (B) an oxyethylation-susceptible,fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin;said resin being derived by reaction between a difunctional monohydricphenol and an aldehyde having not over 8 carbon atoms and having onefunctional group reactive toward said phenol; said resin being formed inthe substantial ab- 15 senceoi phenols of functionality greater than 2;said phenol being of the formula:

. l OH in which R is a hydrocarbon radical having at least 4 and notmore than 12 carbon atoms and substituted in one of the positions orthoand para; said oxyethylated resin being characterized by theintroduction into the resin molecule at the phenolic hydroxyls of aplurality of divalent ,radicals having the formula (Cal-I40); whereinnis a numeral varying from 1 to 20; with the proviso that at least 2moles of ethylene oxide be introduced for each phenolic nucleus; withthe further proviso that thehydrophile properties of the ester as wellas the oxyethylated resin in an equal weight of xylene are sulficient toproduce an emulsion when said xylene solution is shaken vigorously withone to three volumes of water; and with the final proviso that saidblowing of the ester be by means of a gaseous oxygen-containing medium.

4. A blown ricinoleate of certain hydrophile polyhydric syntheticproducts; said hydrophile synthetic products being oxyethylationproducts of (A) ethylene oxide; and (B) an oxyethylationsusceptible,fusible, organic solvent-soluble, water-insoluble, low-stagephenol-aldehyde resin having an average molecular weight correspondingto at least 3 and not over 7 phenolic nuclei per resin molecule; saidresin being derived by reaction between a diiunctional monohydric phenoland formaldehyde; said resin being formed in the substantial absence ofphenols of functionality greater than 2;said phenol being of theformula:

in which R is an aliphatic hydrocarbon radical having at least 4 and notmore than 12 carbon atoms and substituted in one of the positions orthoand para; said oxyethylated resin being characterized by theintroduction into the resin molecule at the phenolic hydroxyls of aplurality of divalent radicals having the formula (C2H4O 11.

wherein n is a numeral varying from 1 to 20; with the proviso that atleast 2 moles of ethylene oxide be introduced for each phenolic nucleus;with the further proviso that the hydrophile properties of the ester aswell as the oxyethylated resin in an equal weight of xylene aresufflcient to produce an emulsion when said xylene solution is shakenvigorously with one to three volumes of water; and with the finalproviso that said blowing of the ester be by means of a gaseousoxygen-containing medium.

5. The product of claim 4, wherein R is substituted in the paraposition.

6. The product of claim 4, wherein R is a butyl radical substituted inthe para position.

7. The product of claim 4, wherein R is an amyl radical substituted inthe para position.

8. The product of claim 4, wherein R is a nonyl radical substituted inthe para position.

MELVIN DE GROOTE. BERNHARD KEISER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS

1. A BLOWN ESTER IN WHICH THE ACYL RADICAL IS THAT OF AN UNSATURATEDFATTY ACID HAVING AT LEAST 8 AND NOT MORE THAN 22 CARBON ATOMS, AND THEALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILE POLYHYDRIC SYNTHETICPRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATIONPRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE,PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE, AND METHYLGLYCIDE; AND (B) ANOXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE,WATERINSOLUBLE, PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BYREACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVINGNOT OVER 8 CARBON ATOMS AND HAVING ONE FUNCTIONAL GROUP REACTIVE TOWARDSAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OFPHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OF THEFORMULA